Process for treating carbonaceous material



Dec. 26, 1933. J. c. MORRELL 1,940,725

PROCESS FOR TREATING CARBONACEOUS MATERIAL Filed Nov. 15 192s gwuanloz alike/am Patented Dec. 26, 1933 PROCESS FOR TREATING CARBONACEOUS MATERIAL Jacque C. Morrell, Chicago,

versal Oil Products Company, corporation of South Dakota 111., assignor to Uni- Chicago, 111., a

Application November 15, 1929 Serial No. 407,379

6 Claims. (01. 196--56) V This invention relates to the treatment of coal, peat, lignite or other bituminous or related substances such as pitches, oil shales, grahamite, albertite and the like. Preferably, these substances are treated in the presence of oils or hydrocarbon substances, generally at elevated temperatures thereby converting the primary products of distillation into lower boiling products through the medium of cracking.

In my process the coal, peat, lignite or other bituminous substances are preferably prepared in a finelydivided form and are preferably admixed with oil or hydrocarbon material, the mixture being raised to an elevated temperature and in some cases under pressure whereby the hydrocarbons undergo conversion to form lower boiling products. Intermediate products may be returned for further, heat treatment and conversion. In my process, I provide means for the accumulation of coke resulting from the process and among the objects of the invention is the production of a marketable coke-like fuel while simultaneously producing a product suitable for motor fuel and a gaseous fuel. The low boiling material and gas. products of the process, may, of course, be used for other purposesfor example, chemical derivatives may be made from them. I also provide means for heating the coal or bituminous material alone or in admixture with oil or hydrocarbon materials in the presence of water, steam or superheated steam and in the presence of hydrogen and various gases which may contain hydrogen such as natural. gas, still gases, producer gas and others. I may also, under certain conditions, utilize air or other oxidizing gases, es-

pecially where a controlled internal combustion as well as controlled oxidation for intermediate derivatives of hydrocarbon such as alcohols, aldehydes, acids etc. as desired.

One of the salient features of the invention is the utilization of the products of combustion or fuel gases as a heating means and in this connection I may use producer gas or superheated steam or other heated gases or vapors such as the hydrocarbon vapors and gases from the cracking process itself alone or in combination with the products of combustion. It will be appreciated that the use of these various mediums in selective combinations permits not only an accurate control of the reaction and its products, but'also aifords a method of modifying'and regulating the temperature conditions and the efiect of each of the mediums. In utilizing the hot hydrocarbon vapors from the cracking process, I may, make use of select intermediate products 'tively high temperatures,

by distributing a cable in the chamber which befrom the cracking process and heat them to relathus converting such hydrocarbons into lower boiling products suitable for motor fuel and preferably having high antiknock value owing to the high temperature conditions under which they have been produced. When utilizing producer gas as a source of heat in whole or in part, I make use of the heat contained in the producer gas as formed or mayimpart additional heat thereto. When utilizing steam it is preferably super-heated. When utilizing hydrogen, I may obtain it from any source whatever, for example, by electrolysis or by the passage of steam through a column of metal which liberates hydrogen from said steam, for example, magnesium, aluminum, zinc, iron, etc. In all of the modifications of the process the principle of direct contact of the heating medium undergoing treatment is employed.

Describing my process in connection with the accompanying drawing, oil is pumped by means of pump 1 through line 2 and valves 3, 4, 5 and 6 into line 7 where it may pass into one of several mixers 8, controlling same by valves 9 to be mixed with coal, peat, lignite or other bituminous materials introduced into the mixers by hoppers 10, said hoppers being arranged internally to avoid leakage of vapors, but permitting the passage of the bituminous material from the feed or storage bins 11. Water, or other fluids, for example, various oils and tars, may be fed through lines 12 controlled by valves 13 into the mixers 8 so as to render the mixture fluid enough to. handle and also to take part in the reaction. From mixers 8 the coal or other bituminous substances admixed with the oil or, in some cases alone, is fed through lines 14 controlled by valves 15 into one or all of chambers 16. The coke formed in the chambers may beremoved by suitable means through the bottom man-head. These chambers, of which there may be a plurality, are arranged to operate in parallel, permitting the diversion of the flow of materials undergoing treatment, in the chamber, from one to the other. When this becomes necessary, for example, when one chamber is full of coke another is put into use and during this period a third may be in preparation. The coke may be removed from the chamber by any suitable method and means, e. g.

comes embedded in the coke which later is removed with the cable by drilllng, etc. The mixture from mixer 8 may also be pumped through line 14' controlled by valves 15' by pumps 8' into the chambers 16. Simultaneously, with the introduction of the charging materials into the chambers 16, the products of combustion from combustion chamber 17 pass through line 18 into any of the chambers 16 through lines 19 by manipulation of valves 21 and 21' in line 18 and valve 20 in lines 19, which permits the heated gases or vapors to be introduced at difierent levels in the chambers. This combustion may take place under pressure to permit feeding the products of combustion into the chambers 16 when it is desirable to maintain a pressure upon same.

The hot products of combustion passing through line 18 may be mixed with oil vapors in mixer 22. In the event that chamber 16 is operated at pressures exceeding atmospheric pressure, which is contemplated in the present invention, it may be necessary to pump the heating gases or vapors by means of pump 23 in line 24 controlled by valves 25 into the mixer 22 through valve 57 and thence to the chambers 16 or direct into the chambers 16 through valve 58 and line 18. The chambers 16 are preferably operated at pressures ranging from atmospheric to 100 pounds per square inch, but pressures up to and exceeding 3000 pounds per square inch may be employed for eiiecting certain reactions contemplated in the process. These high pressures are especially effective in hydrogenating reactions and in speeding up the rate of cracking. In case the chambers 16 are operated at a lower pressure than that at the outlet of coil 54 the gases may by-pass the pump 23 by opening valve 23 and closing valves 25 and the gases may pass to chambers 16 through the mixer 22 or direct as above described. When superheated steam is used as the heating medium in whole or in part it is generated in boiler 26 located in furnace 27 and is then passed through superheater 28, valve 28' into line 18 from where it may finally be introduced into chambers. 16. The superheater simply acts as a conduit when ordinary steam is used. Likewise, when producer gas is used it is made in producer 29 and passed through line 30, valves 31 and 32 into line 18 leading into chambers 16 or the producer gas may be by-passed through valve 31 into superheater 30' through valves 32' and 32 into line 18. Air may be introduced into line 33 controlled by valve 34 or at any point along line. 18 finally leading into chambers 16. Likewise, hydrogen may be introduced into the system by means of line 35 controlled by valve 36 if partial hydrogenation is desired. Either the air or the hydrogen may be heated directly by means not shown.

Any or all of the heating agents or reactants namely combustion gases, saturated or superheated steam, producer gas, heated oil vapors, air

or other oxidizing gas and hydrogen may be introduced under pressure into the chambers 16 in the following manner. The products of combustion may be diverted from line 18 through valve 18" into line 24. Producer gas and/or air or other oxidizing agent may also be introduced into line 24 in the same manner. Hydrogen may enter through line 24 through line 35' controlled by valve 36. Saturated or superheated steam may be diverted into line 24 by opening valve 28" and heated hydrocarbon vapors may pass into'line 24 through valve 25. Any or all of these products in various combinations may pass from line 24 by means of pump 23 through valve 25 into line 55, and from here may pass through valve 57 into the mixer 22 or through valve 58 directly into line 18 and thence to chambers 16 as above described. It is to be understood that several paths and pumps may be used for the above described purposes.

The vapors leave the chambers 16 through lines 37 controlled by valves 38 and 39 where they pass through manifold line 40 into chamber 41. The hot vapors and gases entering chamber 41 are cooled and some of the heavier fractions, condensed by the introduction of relatively cold oil, through pump 1 into line 42 controlled by valve 43. A portion of the raw charging oil vaporized in chamber 41, together with uncondensed vapors and gases entering 41, pass through line 44 controlled by valve 45 into fractionating and/ or dephlegmating column46. The vapors leaving 46 may be passed through line 46" and valve 47" through line 59, condenser 61 into receiver 62 to be cooled, condensed and collected, and the gases later scrubbed for further recovery of condensable material by any suitable means not shown or the vapors from chamber 46 may be passed through line 46' and valve 47 into a secondary tower 47 and further subjected to a fractionating and scrubbing action. The vapors leaving tower 47 pass through line 59 and valve 60 into cooler and condenser 61 where they are cooled and condensed and the liquid is collected in receiver 62. The liquid collecting in 62 is removed through valve 63 and pumped to storage. A portion of the condensate may be returned for cooling in towers 46 and 47 by introducing it through pump 62', lines 63 and 64' and valves 65' and 66'. The gases pass thru line 64 controlled by valve 64 and may be burned as fuel or otherwise disposed of A portion of the gases may be recirculated through line 66 and valves 67 and may be introduced through line 68 and valves 67 and 69' into the bottom of chamber 41 or may be introduced into the top of chamber 41 through line 68 and valve 69. Pump 77 shown on by-pass line 78 equipped with valves 79 may be used for this purpose if necessary. The gas may also be passed to the heating coil 54 through line 66 and valves 67 and 80 to be recirculated through chambers 16 via line 55 and valve 56. The gases leaving the process may contain a substantial portion of suspended liquid materiaL and in order to recover this valuable product it is contemplated treating the gases by various methods such as scrubbing, compression, etc. It is also contemplated making use of such heat exchange devices as desired or necessary in carrying out the process.

The condensed reflux from tower 46 passes through line 48 and the reflux from tower 47 passes through line 49 and valve 50. The reflux from either or both towers 46 or 47 may be pumped by pump 51 through line 52 and valve 53 into heating coil 54, or may be drawn off for other uses through line 49', valve 50'. Also a portion of the charging stock from line 2 may be introduced to heating coil 54 through line 2 having valve 4 and thence into chambers 16. The reflux oil alone or admixed with charging stock or charging stock alone entering heating coil 54 may be heated to any temperature desiredpreferably to a convers'on temperature wherein a substantial amount of cracking occurs and in many cases it is desirable to raise the temperature within this heating coil so that so-called vapor-phase cracking or high temperature conversion occurs. The pressure in this coil may range from atmospheric up to 1500 pounds more or less. The vapors leaving heating coil 54 pass through line 55 and pressure control valve 56 electric precipitation, :32.

' into mixer 22 through valve 57 or direct into line 18 by means of valve 58 or in the manner already described.

The non-vaporized residue from chamber 41 is withdrawn through line 70 and may be passed to storage through valve 71 after cooling if necessary, or may be passed through valve 72 and pumped by means of pump 73 through valve '74 and line '70 and into the mixers 8 through valves 6 and 9 and line 7 or directly into the chambers 16 by means not shown. A portion of the reflux from towers 46 and 47 may be passed from line 52 through valve 75 into line 2 to be blended with the charging stock. Likewise, a portion of this reflux may be withdrawn through valve 75' and line '76 to be blended with the residue directly withdrawn from chamber 41.

As an example of the operating conditions and results obtainable by my process, a mixture of bituminous coal in a finely divided state and suflicient oil to render it a thin paste was treated using combustion gases as a heating medium. The reflux from fractionating columns 46 and 47 was cracked in heating coil 54 to supply further heat and to increase the yield of motor fuel. Under these conditions a yield of approximately 6 gallons of motor fuel per ton of coal processed can be obtained in addition to approximately 50% of motor fuel by volume of the oil fed to the process. The oil considered in this example is an 18 A.P.I. gravity fuel residue. Using a mixture of approximately equal parts of coal and oil by weight approximately forty percent of distillate by weight of the mixture containing of motor fuel based on the volume of the distillate and approximately 60% of coke and gas based on the raw mixture was obtained. The temperature of the combustion gases entering coking chambers 16 may be approximately 2500 F. The temperature of the hydrocarbon oil leaving heating coil 54 may be approximately 1050 F. The distillate collected in distillate receiver 62 when refined with sulphuric acid, caustic and the usual reagents and redistilled in the presence of steam produces a high antiknock motor fuel. The introduction of steam with the combustion gases as a heating medium reduces the total amount of tar acids compared with a heating medium where steam was not used and increased the yield of neutral oils. The gases from the process contained a. larger amount of hydrogen when steam was used. The coke produced in this process will be suitable as a fuel, the volatile matter remaining, depending upon the temperature and time of treatment.

While I have given an example of the process it is to be understood that the details set forth are purely illustrative and are not to be construed as a limitation on the broad scope and spirit of the invention.

I claim:-

1. A process for producing hydrocarbon distillates from solid bituminous material and heavy hydrocarbon oil which comprises mixing a portion of the heavy oil with the solid material and placing the mixture in an enlarged distillation zone, heating another portion of the heavy oil unadmixed with solid material to vapor phase cracking temperature of the order of about 1000 F. in an independent zone, introducing the resultant vapor phase cracked vapors into said distillation zone to supply heat for the distillation of said mixture, distilling the mixture in said distillation zone, and removing and condensing resultant vapors.

2. A process which comprises distilling a body of solid bituminous material in an enlarged zone, removing resultant vapors and subjecting the same to dephlegmation to condense heavier fractions thereof, heating the condensed heavier fractions unadmixed with solid material to vapor phase cracking temperature of the order of about 1000 F. in an independent zone, introducing the resultant vapor phase cracked vapors to said enlarged zone to supply heat for the distillation of the solid material therein, and condensing the dephlegmated vapors as a product of the process.

3. A process which comprises distilling a mixture of solid bituminous material and heavy hydrocarbon oil in a distillation zone, removing resultant vapors and dephlegmating the same to condense heavier fractions thereof, heating the condensed heavier fractions unadmixed with solid material to vapor phase cracking temperature of the order of about 1000 F. exteriorly of said zone and then introducing the resultant vapor phase cracked vapors into said mixture to. I

provide heat for the distillation thereof, an condensing the dephlegmated vapors.

4. A method which comprises charging a mass of solid bituminous material to a distillation zone, cracking a hydrocarbon oil in the vapor phase at a temperature of the order of about 1000 F. exteriorly of said zone, introducing the vapor phase cracked vapors while at high temperature to said zone to supply heat for the distillation of the material therein, distilling the solid material in said zone, removing and dephlegmating the resultant mixture of vapor phase cracked vapors and vapors evolved from the solid material, and utilizing resultant reflux condensate as said hydrocarbon oil.

5. A method which comprises charging a mass of solid bituminous material to a distillation zone, cracking a heavy hydrocarbon oil in the vapor phase at a temperature of the order of about 1000 F. exteriorly of said zone, introducing the vapor phase cracked vapors while at high temperature to said zone to supply heat for the distillation of the material therein, distilling the solid material in said zone, removing the resultant vapors from said zone and subjecting the same to dephlegmation to condense heavier fractions thereof, utilizing the condensed heavier fractions to constitute at least a part of said hydrocarbon oil being vapor phase cracked, and condensing the dephlegmated vapors as a product of the process. 4

6. A process which comprises distilling a mixture of solid bituminous material and hydrocarbon oil by direct contact with a gaseous heating medium in a distillation zone, simultaneously cracking a hydrocarbon oil in the vapor phase at a temperature of the order of about 1000 F. exteriorly of said zone, introducing the vapor phase cracked vapors into said zone to constitute at least a part of said heating medium, and removing the mixed vapors from said zone for con- 

